The present invention generally relates to monoarylide pigment compositions. In particular, the present invention relates to monoarylide pigments coupled in the presence of hydrocarbyl polyamines which provide pigment compositions having increased tinctorial strength.
Azo pigments are a class of colorants that are relatively strong tinctorially and relatively inexpensive. Azo pigments are generally either monoazo or disazo pigments. Azo pigments can also be classified by the type of coupler used (e.g., acetoacetarylide or arylide, pyrazolone, or 2-naphthol). Monoazo pigments made by coupling into an acetoacetarylide are called monoarylide pigments.
Monoarylide pigments generally show good lightfastness/weathering resistance and are particularly useful as coloring agents for paints. One particular use of reddish yellow monoarylide pigments includes replacement for medium chrome yellow pigments in paints used to make traffic stripes. Although monoarylide pigments are relatively strong tinctorially, they are not as tinctorially strong as diarylide pigments. For example, monoarylide yellow C.I. (Colour Index) P.Y. (Pigment Yellow) 65 is not as tinctorially strong as diarylide yellow C.I. P.Y. 83. W. Herbst and K. Hunger, Industrial Organic Pigments, Second Edition, VCH, New York, 1997, p. 228, state: xe2x80x9cTinctorially, however, P.Y. 65 is considerably inferior, which precludes its application in printing inks. Opaque varieties of the slightly more greenish diarylide yellow pigment P.Y. 83, for instance, are more than three times as strong as P.Y. 65, yet provide similar lightfastness.xe2x80x9d
A patent which describes coupling monoarylide yellow pigments in the presence of monoamine salts, followed by addition of rosin solutions, is German Offenlegungsschrift 2526872 (1976, Ciba-Geigy AG); this process gives pigments with increased dispersibility and transparency in lithographic inks.
Several patents describe coupling diarylide yellow pigments in the presence of amine salts. U.S. Pat. No. 5,672,202 to Stirling et al relates to coupling diarylide yellow C.I. P.Y. 12 in the presence of a long chain aliphatic primary amine and ethylene polyamine, then post-adding (adding after coupling) quaternary ammonium chloride and a long chain aliphatic dipropylenetriamine to improve strength, gloss and transparency. U.S. Pat. No. 5,145,997 to Schwartz et al relates to co-coupling P.Y. 12 with a (acetoacet) derivative of a polyoxyalkylene mono-, di- or tri-amine, which gave gravure inks with less color deterioration than inks containing P.Y. 12 modified with tallowalkyl dipropylenetriamine. U.S. Pat. No. 4,885,033 to Blackburn et al relates to coupling P.Y. 12 in the presence of 2,2xe2x80x2-disulfobenzidine dyes and rosin salts, then mixing it with a P.Y. 13/tallowalkyl propylenediamine mixture to improve rheology and printing properties of inks. European Patent 567,918 (1994, Hoechst AG) relates to coupling P.Y. 12 in the presence of an amide of tallowalkyl propylenediamine and caprolactam along with bis(4-aminocyclohexyl)methane and a long chain aliphatic amine to improve gloss, strength and holdout. European Patent 62,304 (1982, Hoechst AG) relates to coupling diarylide yellows in the presence of a long chain aliphatic amine or a quaternary ammonium chloride phase transfer catalyst, then post-adding a polyethyleneamine to increase strength and gloss. U.S. Pat. No. 4,462,833 to Hays et al relates to post-adding tallowalkyl tripropylenetetramine to P.Y. 12 slurries to increase holdout of publication gravure inks.
The present invention provides monoarylide pigments with excellent tinctorial strength. Since monoarylide pigments tend to be less expensive and have better lightfastness/weathering resistance than diarylide pigments, increasing the tinctorial strength of monoarylide pigments is a very attractive benefit associated with the present invention.
One aspect of the invention relates to pigment composition containing a monoarylide pigment and a hydrocarbyl polypropyleneamine compound. Another aspect of the invention relates to making an monoarylide pigment involving coupling a substituted or unsubstituted acetoacetanilide with at least one diazotized aromatic amine in a solution containing a hydrocarbyl polypropyleneamine. Yet another aspect of the invention relates to paint, ink, electrostatic toner, powder coating, and paper compositions containing the pigment composition or monoarylide pigment made in accordance with the invention.
The present invention relates to a monoarylide pigment made using one or more hydrocarbyl polypropyleneamine compounds. In this connection, monoarylide pigments in accordance with the present invention are made, in part, by coupling a diazotized aromatic amine with a substituted or unsubstituted acetoacetanilide in the presence of at least one hydrocarbyl polypropyleneamine. Pigment compositions contain the monoarylide pigment and the hydrocarbyl polypropyleneamine. Although not limited thereto, monoarylide pigments in accordance with the present invention typically have yellow and/or orange color.
The pigments of the present invention are made using or pigment compositions of the present invention contain a hydrocarbyl polypropyleneamine having Formula (I):
RNH(CH2CH2CH2NH)xHxe2x80x83xe2x80x83(I)
wherein R is a saturated or unsaturated hydrocarbyl group containing about 10 or more carbon atoms and about 24 or less carbon atoms and x is about 1 or more and about 5 or less. In another embodiment, R is a saturated or unsaturated hydrocarbyl group containing about 12 or more carbon atoms and about 22 or less carbon atoms and x is about 2 or more and about 4 or less. In yet another embodiment, R is a saturated or unsaturated hydrocarbyl group containing about 14 or more carbon atoms and about 20 or less carbon atoms.
As used herein, the term xe2x80x9chydrocarbylxe2x80x9d means that the group being described has predominantly hydrocarbon character within the context of this invention. These include groups that are not only purely hydrocarbon in nature (containing only carbon and hydrogen), but also groups containing substituents or hetero atoms which do not alter the predominantly hydrocarbon character of the group. Such substituents may include halo-, carbonyl-, ester-, ether-, alkoxy-, nitro-, etc. These groups also may contain hetero atoms. Suitable hetero atoms will be apparent to those skilled in the art and include, for example, sulfur, nitrogen and particularly oxygen.
In one embodiment, the hydrocarbyl polypropyleneamine is a saturated alkyl polypropyleneamine, wherein the alkyl group contains about 10 or more carbon atoms and about 24 or less carbon atoms. In another embodiment, the hydrocarbyl polypropyleneamine is an unsaturated alkyl polypropyleneamine, wherein the alkyl group contains about 10 or more carbon atoms and about 24 or less carbon atoms.
General examples of hydrocarbyl polypropyleneamines include stearyl poly(propyleneamine), oleyl poly(propyleneamine), lauryl poly(propyleneamine), decyl poly(propyleneamine), myristyl poly(propyleneamine), palmyl poly(propyleneamine), isodecyl poly(propyleneamine), tallowalkyl poly(propyleneamine), and cocoalkyl poly(propyleneamine).
Specific examples of hydrocarbyl polypropyleneamines include tallowalkyl tetrapropylenepentamine, tallowalkyl tripropylenetetramine, tallowalkyl dipropylenetriamine, cocoalkyl tetrapropylenepentamine, cocoalkyl tripropylenetetramine, cocoalkyl dipropylenetriamine, stearyl tetrapropylenepentamine, stearyl tripropylenetetramine, stearyl dipropylenetriamine, oleyl tetrapropylenepentamine, oleyl tripropylenetetramine, oleyl dipropylenetriamine, lauryl tetrapropylenepentamine, lauryl tripropylenetetramine, lauryl dipropylenetriamine, decyl tetrapropylenepentamine, decyl tripropylenetetramine, decyl dipropylenetriamine, myristyl tetrapropylenepentamine, myristyl tripropylenetetramine, myristyl dipropylenetriamine, palmyl tetrapropylenepentamine, palmyl tripropylenetetramine, palmyl dipropylenetriamine, isodecyl tetrapropylenepentamine, isodecyl tripropylenetetramine, and isodecyl dipropylenetriamine.
Hydrocarbyl polypropyleneamines include those under the trade designation Corsamine available from Corsicana Technologies, Inc., and specifically product designations PNT, TET and TRT; those available from Akzo Nobel Chemicals Inc. under the trade designations Tetrameen T and Triameen T; and those under the trade designation Polyram(copyright) available from Ceca S. A.
The hydrocarbyl polypropyleneamines are typically insoluble in water, so they can be made soluble, if necessary, by dissolving in an acidic solutions of acetic acid, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and the like. After coupling (subsequently described), the soluble protonated hydrocarbyl polypropyleneamines may be precipitated on the pigment by addition of a strong base, such as sodium hydroxide, potassium hydroxide, and the like, which promotes flocculation of the pigment dispersion and allows filtration and washing. Monoarylide pigments in accordance with the present invention are represented by compounds having Formula (II): 
wherein each R1 and each R2, if any, are independently halogen, an alkyl group having 1 to about 4 carbon atoms, an alkoxy group having 1 to about 4 carbon atoms, an alkoxycarbonyl group having 1 to about 6 carbon atoms, a nitro group, a cyano group, a phenoxy group, or a trifluoromethyl group, and n and y are independently 0 or more and 4 or less. In another embodiment, each R1 and each R2, if any, are independently halogen, an alkyl group having 1 to about 3 carbon atoms, an alkoxy group having 1 to about 3 carbon atoms, a nitro group, and n and y are independently 1 or more and 3 or less. Halogens include fluorine, chlorine and bromine. The monoarylide pigments in accordance with the present invention are made, in part, by coupling a diazotized aromatic amine with a substituted or unsubstituted acetoacetanilide in the presence of at least one hydrocarbyl polypropyleneamine.
Specific examples of monoarylide pigments in accordance with the present invention include P.Y. 3 (wherein a first R1 in the 2-position is nitro, a second R1 in the 4-position is chloro, and an R2 in the 2-position is chloro), P.Y. 65 (wherein a first R1 in the 2-position is nitro, a second R1 in the 4-position is methoxy, and an R2 in the 2-position is methoxy), and P.O. 1 (wherein a first R1 in the 2-position is nitro, a second R1 in the 4-position is methoxy, and an R2 in the 2-position is methyl).
Aromatic amines are compounds generally represented by Formula (III): 
wherein each R1 is independently halogen, an alkyl group having 1 to about 4 carbon atoms, an alkoxy group having 1 to about 4 carbon atoms, an alkoxycarbonyl group having 1 to about 6 carbon atoms, a nitro group, a cyano group, a phenoxy group, or a trifluoromethyl group, and n is 0 or more and 4 or less. In another embodiment, each R1 is independently halogen, an alkyl group having 1 to about 3 carbon atoms, an alkoxy group having 1 to about 3 carbon atoms, a nitro group, and n is 1 or more and 3 or less.
In yet another embodiment, aromatic amines are nitro compounds represented by Formula (IV): 
wherein each R1 is independently halogen, an alkyl group having 1 to about 4 carbon atoms, an alkoxy group having 1 to about 4 carbon atoms, an alkoxycarbonyl group having 1 to about 6 carbon atoms, a cyano group, a phenoxy group, or a trifluoromethyl group, and n is 0 or more and 3 or less. In another embodiment, each R1 is independently halogen, an alkyl group having 1 to about 3 carbon atoms, an alkoxy group having 1 to about 3 carbon atoms, and n is 1 or more and 2 or less.
Examples of commonly available aromatic amines characterized by Formulae (III) and/or (IV) include 2-methoxy-4-nitroaniline; 2-methoxy-5-nitroaniline; 4-methoxy-2-nitroaniline; 2-amino-4-chloro-5-nitrotoluene; 2-chloro-4-nitroaniline; 2-chloro-5-nitroaniline; 4-chloro-2-nitroaniline; 4-chloro-3-nitroaniline; 5-chloro-2-nitroaniline; 5-chloro-2-methyl-4-nitroaniline; 2-chloro-4-methylaniline; 2-chloro-5-methylaniline; 2-chloro-6-methylaniline 3-chloro-2-methylaniline; 3-chloro-4-methylaniline; 4-chloro-2-methylaniline; 5-chloro-2-methylaniline; 4-chloro-2-methoxy-5-methylaniline; 4-chloro-2,6-dinitroaniline; 6-chloro-2,4-dinitroaniline; 2-chloro-4,6-dimethylaniline; 3-chloro-2,6-diethylaniline; 4-chloro-2,6-dibromoaniline; 2-chloroaniline; 3-chloroaniline; 4-chloroaniline; 5-chloro-2-methoxyaniline; 3-chloro-4-methoxyaniline; aniline; and the like.
Substituted or unsubstituted acetoacetanilides are compounds generally represented by Formula (V): 
wherein each R2 is independently halogen, an alkyl group having 1 to about 4 carbon atoms, an alkoxy group having 1 to about 4 carbon atoms, an alkoxycarbonyl group having 1 to about 6 carbon atoms, a nitro group, or a phenoxy group, and y is 0 or more and 4 or less. In another embodiment, each R2 is independently halogen, an alkyl group having 1 to about 3 carbon atoms, an alkoxy group having 1 to about 3 carbon atoms, a nitro group, and y is 1 or more and 3 or less.
Examples of acetoacetanilides include acetoacetanilide, acetoacet-2-methoxyanilide, acetoacet-4-methoxyanilide, acetoacet-2-methylanilide, acetoacet-4-methylanilide, acetoacet-2,4-xylidide, acetoacet-2-chloranilide, acetoacet-2,5-dimethoxy-4-chloranilide, and the like.
The pigments of the present invention may be prepared by initially diazotizing the aromatic amine wherein the aromatic amine forms a diazonium component, and coupling the diazonium component with a coupling component comprised of an acetoacetanilide coupler in the presence of at least one hydrocarbyl polypropyleneamine. The coupling may be conducted in an acidic solution of at least one hydrocarbyl polypropyleneamine.
The aromatic amines from which the diazonium components are prepared are available commercially or can be prepared using methods known in the art. The diazotization of the aromatic amines useful for the purposes of this invention may be carried out in the manners known to those skilled in the art. For example, diazotization may be carried out through the use of alkali metal nitrites or lower alkyl nitrites together with an adequately strong acid such as a mineral acid. Examples of useful mineral acids include hydrochloric acid and sulfuric acid. Nitrosyl sulfuric acid also can be utilized. The diazotization reaction can be conducted at a temperature in the range from about xe2x88x9220xc2x0 C. to about 30xc2x0 C., preferably from about 0xc2x0 C. to about 20xc2x0 C.
In one embodiment, it is advantageous in the diazotization reactions (and in the subsequent coupling reactions) to include one or more appropriate organic solvents. For example, suitable organic solvents include one or more of glacial acetic acid, lower alkanols, dioxane, formamide, dimethyl formamide, dimethyl sulfoxide, pyridine or N-methyl pyrrolidone. In another embodiment, it is advantageous in the diazotization reactions (and in the subsequent coupling reactions) not to include one or more organic solvents.
The coupling reaction useful for the purposes of the present invention may be effected preferably by adding the diazonium components to the coupling components, but the coupling components can be added to the diazonium components. Coupling is generally effected at a temperature of from about xe2x88x9220xc2x0 C. to about 80xc2x0 C., preferably from about 10xc2x0 C. to about 40xc2x0 C. As in the diazotization reaction, coupling may be carried out in the presence or absence of an suitable organic solvent, such as all of those identified above in connection with the diazotization reaction.
The coupling reaction solution or slurry generally has an acidic or neutral pH. For example, in one embodiment, the coupling reaction solution has a pH of about 3 or more and about 7 or less. In another embodiment, the coupling reaction solution has a pH of about 4 or more and about 6 or less. In yet another embodiment, the coupling reaction solution has a pH of about 4.25 or more and about 6.5 or less.
In another embodiment, generally, the diazonium components are coupled with a slight stoichiometric excess of the coupling component. That is, one equivalent of the diazonium components (total amount of the diazonium components) is coupled with slightly more than one equivalent of the coupling component. In one embodiment, the ratio of equivalents of the diazonium components to the coupling component is from about 0.9:1 to about 1:1. In another embodiment, the ratio of equivalents of the diazonium components to the coupling component is from about 0.95:1 to about 1:1 and preferably from about 0.98:1 to about 1:1.
In another embodiment of the present invention, the dispersibility of the pigments of the present invention can be improved by adding alkali-soluble resin-like products before, during, or after the coupling is completed. Various resin-like materials can be added for this purpose, and these include for example, rosin resins, polymeric rosins, resin soap, chemically modified rosin resins, such as rosin-maleinate resins, alkyd resins, and other synthetic hydrocarbon resins with a higher acid number, or combination of these resins. The resins may be present in a product with free carboxyl groups that are capable of forming a salt, or may be partially or completely in the form of salts, for example, with alkali metal ions. It may also be advantageous to perform the coupling reaction in the presence of a finely divided insoluble material, for example, alkaline earth metal sulfates and carbonates, titanium dioxide or clay materials or very finely divided organic plastic materials.
The coupling reaction of the present invention is conducted in a solution or slurry in the presence of at least one hydrocarbyl polypropyleneamine. In one embodiment, the solution in which coupling occurs contains at least one hydrocarbyl polypropyleneamine in an amount of about 1% by weight or more and about 25% by weight or less based on the weight of the monoarylide pigment. In another embodiment, the solution in which coupling occurs contains at least one hydrocarbyl polypropyleneamine in an amount of about 2.5% by weight or more and about 20% by weight or less based on the weight of the monoarylide pigment. In yet another embodiment, the solution in which coupling occurs contains at least one hydrocarbyl polypropyleneamine in an amount of about 5% by weight or more and about 15% by weight or less based on the weight of the monoarylide pigment.
In most applications, it is desirable, in order to achieve the full brightness and tinctorial strength, to heat the monoarylide pigment. For example, the monoarylide pigment may be heated to boiling temperature for about 0.25 to about 3 hours at temperatures about 100xc2x0 C. or higher optionally under pressure in the presence or absence of the above-described resin soaps or other soluble resins.
After completion of the reactions and optional heating, the finely divided dispersion of monoarylide pigment and acidic solution of hydrocarbyl polypropyleneamine is flocculated by addition of a strong base to raise the pH to about 10 to about 11; this high pH precipitates the hydrocarbyl polypropyleneamine and changes the fine dispersion to a coarse slurry.
The monoarylide pigments are recovered from the water-based reaction slurry by filtering to form a presscake of pigment which is washed with cold water or hot water (e.g., from about 40xc2x0 C. to about 70xc2x0 C.), so as to remove the excess acids, bases and unwanted salts formed during the coupling reaction. The presscake is typically washed with from about 10 to about 20 times its volume of hot water. The filter cake is generally washed until the filtrate gives only a slightly positive test for chloride ion. The washed presscakes can be dried, ground and used in the form of a coarse or finely divided powder. Alternatively, the monoarylide pigments of this invention can be dispersed into oleoresinous vehicles to prepare flushed bases or dispersed into aqueous or organic vehicles to prepare aqueous dispersions or organic pigment compositions.
As stated above, the monoarylide pigments in accordance with the present invention are represented by Formula (II). In another embodiment, monoarylide pigments in accordance with the present invention are compounds represented by Formula (VI) 
wherein each R1 and each R2, if any, are independently halogen, an alkyl group having 1 to about 4 carbon atoms, an alkoxy group having 1 to about 4 carbon atoms, an alkoxycarbonyl group having 1 to about 6 carbon atoms, a nitro group, a cyano group, a phenoxy group, or a trifluoromethyl group, y is 0 or more and 4 or less, and n is 0 or more and 3 or less. In yet another embodiment, each R1 and each R2, if any, are independently halogen, an alkyl group having 1 to about 3 carbon atoms, an alkoxy group having 1 to about 3 carbon atoms, a nitro group, y is 1 or more and 3 or less, and n is 1 or more and 2 or less.
The pigment compositions of this invention contain at least one monoarylide pigment and at least one hydrocarbyl polypropyleneamine. In one embodiment, the pigment compositions contain about 90% by weight or more and about 99.99% by weight or less of at least one monoarylide pigment and about 0.01% by weight or more and about 10% by weight or less of at least one hydrocarbyl polypropyleneamine. In another embodiment, the pigment compositions contain about 95% by weight or more and about 99.9% by weight or less of at least one monoarylide pigment and about 0.1% by weight or more and about 5% by weight or less of at least one hydrocarbyl polypropyleneamine.
The pigment compositions of this invention provide high quality monoarylide pigments having improved color/tinctorial strength, and are useful as coloring agents in paints, inks, electrostatic toners, powder coatings, and papers. This invention, therefore, also relates to paint, ink, electrostatic toner, powder coating, and paper compositions comprising major amounts of a paint vehicle, ink vehicle, electrostatic toner vehicle, powder coating vehicle, and paper vehicle and minor amounts of the monoarylide pigment compositions of this invention. In a preferred embodiment, the invention relates to paints comprising the monoarylide pigment composition. Major amounts include at least 50% by weight whereas minor amounts include less than 50% by weight.
The paint, ink, electrostatic toner, powder coating, and paper compositions in which the pigments of this invention are useful are well known to those of ordinary skill in the art. Examples of inks include printing inks, gravure inks and lacquers. The monoarylide pigment compositions are also useful for pigment printing and for the pigmenting of paper in the mass, electrostatic toners, and powder coatings.
Due to its excellent color/tintorial strength, the monoarylide pigments are particularly suitable for the pigmenting of paints, such as, for example, latex paints, alkyd paints, epoxy paints, oil based paints, road paints (generally for use on asphalt and cement), and the like.
See, for example, with regard to ink: R. H. Leach, editor, The Printing Ink Manual, Fourth Edition, Van Nostrand Reinhold (International) Co. Ltd., London (1988), particularly pages 282-591; and with regard to paints: C. H. Hare, Protective Coatings, Technology Publishing Co., Pittsburgh (1994), particularly pages 63-288. The foregoing references are hereby incorporated by reference herein for their teachings of ink and paint compositions, formulations and vehicles in which the compositions of this invention may be used including amounts of colorants.